Triazine herbicides

ABSTRACT

TRIAZINE COMPOUNDS REPRESENTED BY THE STRUCTURAL FORMULA:   2-(R&#39;&#39;-NH-),4-(R-(CH2)N-NH-),6-X-S-TRIAZINE   WHEREIN X IS ONE SELECTED FROM THE GROUP CONSISTING OF CL, BR, N3, C1-C6 THIOALKYL, C2-C6 ALKYLTHIOALKYLTHIO, C2-C6 ALKYLSULFONYLALKYLTHIO, C2-C6 ALKYLSULFOXYALKYLTHIO, C2C6 ALKOXYALKYLTHIO, C1-C6 CHLOROALKYLTHIO, C1-C6 BROMOALKYLTHIO, C1-C6 ALKOXY, C2-C6 ALKYLTHIOALKYLOX, C2-C6 ALKYLSULFONYLALKYLOXY, C2-C6 ALKOXYALKYLOXO, C1-C6 CHLOROALKYLOXO, C1-C6 BROMOALKYLOXO, R&#39;&#39; IS HYDROGEN, C1-C5 ALKYL, C3-C6 CYCLOALKYL OR C4-C8 ALKYLCYCLOALKYL WITH THE PROVISO THAT THE RING MAY CONTAIN AT LEAST ONE HETERO ATOM SUCH AS NITROGEN, OXYGEN OR SULFUR, N IS AN INTEGER RANGING FROM 1 TO 6, R IS A 5 OR 6 MEMBER RING CONTAINING 1 OR MORE HETERO ATOMS, SAID RING BEING ONE SELECTED FROM THE GROUP CONSISTING OF THE FOLLOWING: R&#34;&#39;&#39;-TETRAHYDROFURYL, R&#34;&#39;&#39;-FURYL, R&#34;&#39;&#39;-TETRAHYDROTHIENYL, R&#34;&#39;&#39;-THIENYL, 1-(CH3-(CH2)N-),R&#34;&#39;&#39;-PYRROLIDINYL, R&#34;&#39;&#39;-TETRAHYDROPYRANYL, R&#34;&#39;&#39;-PYRIDINYL, 1-(CH3-(CH2)N-),R&#34;&#39;&#39;-PIPERIDINYL WHEREIN R&#39;&#39;&#34; IS ONE SELECTED FROM THE GROUP CONSISTING OF H, R1-C6 ALKYL, C3-C6 ALKENYL, C1-C6 HALOALKYL, CL, BR, AND NO2, WHEREIN N IS AN INTEGER RANGING FROM 0 TO 3. SUCH COMPOUNDS HAVE SHOWN OUTSTANDING PRE- AND POSTEMERGENCE HERBICIDAL ACTIVITY.

United States Patent US. Cl. 260249.6 21 Claims ABSTRACT OF THEDISCLOSURE Triazine compounds represented by the structural formula:

wherein X is one selected from the group consisting of Cl, Br, N C -Cthioalkyl, C -C alkylthioalkylthio, C -C alkylsulfonylalkylthio, C -Calkylsulfoxyalkylthio, C C alkoxyalkylthio, C -C chloroalkylthio, C -Cbromoalkylthio, C -C alkoxy, C -C alkylthioalkyloxo, C -Calkylsulfonylalkyloxo, C -C alkoxyalkyloxo, C -C chloroalkyloxo, C -Cbromoalkyloxo; R is hydrogen, C -C alkyl, C -C cycloalkyl or C -Calkylcycloalkyl with the proviso that the ring may contain at least onehetero atom such as nitrogen, oxygen or sulfur; n is an integer rangingfrom 1 to 6; R is a 5 or 6 member ring containing 1 or more heteroatoms, said ring being one selected from the group consisting of thefollowing:

((EHzh-CHa z)n Ha wherein R is one selected from the group consisting ofH, C -C alkyl, C -C alkenyl, C -C haloalkyl, Cl, Br, and N0 wherein n isan integer ranging from 0 to 3. Such compounds have shown outstandingpreand post- 'emergence herbicidal activity.

The present invention is concerned with new compositions for influencingand, more particularly, inhibiting the growth of plants and with themethods of applying these compositions for influence in the growth ofplants. In one aspect, this invention relates to triazines substitutedwith a saturated or unsaturated (5 or 6 membered) hetero- 3,753,986Patented Aug. 21, 1973 "ice methylthio-s-triazine (Ametryne) which arecovered in US. Pat. 2,909,420. f"

More recently, 2 chloro-4-alkylamino-6-cyclopropylamino-s-triazines wereclaimed in US. Pat. 3,451,802. The claim is based on the particularlygood post-emergent herbicidal activity and selectivity exhibited bytriazines with a cyclopropylamino group, which is not found with closelyrelated substituents, such as the cyclopropylmethylamino group. a

The surprising observation has been made that diaminos-triazinederivatives of the general formula:

wherein X is one selected from the group consisting of Cl, Br, N C -Cthioalkyl, C C alkylthioa1kylthio,C C al-kylsulfonylalkylthio, C -Calkylsulfoxyalkylthio, C C alkoxyalkylthio, C -C chloroalkylthio, C -Cbromoalkylthio, C -C alkoxy, C -C alkylthioalkyloxo, C -Calkylsulfonylalkyloxo, C -C alkoxyal'kyloxo, C -C chloroalkyloxo, C -Cbromoalkyloxo; R is hydrogen, C -C alkyl, C -C cycloalkyl oralkylcycloalkyl with the proviso that the ring is capable of containingat least one hetero atom such as nitrogen, oxygen or sulfur; n is aninteger ranging from 1 to 6; R is a five or six member ring containing 1or more hetero atoms, said ring being one selected from the groupconsisting of the following:

Bil/f j Bil/ j" Ell/ t i, nfll k o o s s R!!! I R!!! I R!!! R!!! N 0 N 2r; 6

Huron. Drwherein R is one selected from the group consisting of H, C -Calkyl, C -C alkenyl, C -C haloalkyl, Cl, Br. and N0 wherein n is aninteger ranging from 0 to 3, possess especially good herbicidal activitywith selectivity on some crops. This activity is unexpected sincecycloalkylalkylamino-triazines disclosed in US. 3,451,802 have beenknown not to show significant herbicidal activity.

Exemplary compounds corresponding to the above formula are as follows:

tr zine. (9)2-eyclopropyhnethylamlnol-rnethoxy-G-tetrahydrofuriurylamlno-s-trlazine.(10) 2ch10ro-4-ethylaminofi-tetrahydrofuriurylaminos-trlazine; (l1)2-chilorion-4-isopropylamino-6-tetrahydrofurfurylamino-s- (13)2-sec-butylamino-4chloro-fi-tetrahydrofurfurylammo-s trizaine.

(14) 2-ch1oro-4-methy1amino-6-tetrahydrofuriurylamino-s-triazlne.

(15)2-0hloro+eyc1opropylmethylamino-fi-tetrahydroturfurylamino-s-triazine.

(16) 2-azidmi-ethylarnino-fi-tetrahydrofurfurylamino-s-trlazine.

(17) 2-azido-4-isoprpoylamino-6-tetrahydrofurfurylamlno-s-triazine.

(18) Z-(methylthiomethylthio)-4-ls0propy1amino-G-tetrahydrofur- Vfurylamino-s-triazine.

(19)2-(methylthioethylthio)-4-isopropylamin06-tetrahydrofurfurylamino-s-trlaziue.

TABLE-Continued Cpd. N o. (20;2-chloro-4,6-bis(tetrahydroturturylamlno)-s-trlazine.. (212-methoxy-4,6-bis(tetrahydroniriurylamino)-s-triazine. (22).2-ethylamino-4- urfurylamino-fi-methylthio-s-trlazlne. (23)2-ethylamino-4-furiurylamino-G-methoxy-s-triazine. (24)2-tert-butyl-4-furfi1rylamino-omethoxy-s-tflazine.

(25) Z-t'urturylamino4-methoxy-6methylamino-s-trlazlne.

(28) 2-chloro-4-furturylamino-6-methylamino-s-triazine.

(29) 2-chloro4,6bis-(Z-thienylmethylamino)-s-trlazine.

(30) 2-etrryalannno-4rmethoxy-fi-l2-(2-tetrahydrofuranyl)ethylamino]szine.

(32) 2-azid0-4-neopentylamlno-6-tetrahydroiurfurylaminos-trlazine. (33)2-chloro-4-lsopropylamino-6-(2-thiolanylmethylamlno) -striazlne. (34)2-1;;ethgy-4qnethylamino-d (2-thiolanylmethy1amlno) -siaz e. (35)2-etiziaylialmlno-4-methylthlo-6-(2-thlolanylmethylamino) s e. (36)2-chloro-4-ethylamino-G-(2-thlenylmethy1amino) -s-triazine. (37)Z-tert-butylamino-Qmethoxy-G- (2-thienylmethylamino) -strlazine. (38)2-Itnrth yla1nino-4methylthio-6-(Z-thienylmethylamino) -sazure. (39)2-azidHem-butylamino-fi-[Z-(tetrahydropyranyl) -methylamlnol-s-trlazine.(40) 2-methoxy-4methylamlno-6-[2- (tetrahydropyranyl)-methylamino1-s-triazine. (41)2-tert-butylamino-4-methylth1o-6-[2-(tetrahydropyranyl)methylamlno1-s-triazine.

, (42) 2-lsoamylamino-4-chloro-6-(a-picolinylarnino)-s-trlazine.

(43) 2-ethylemino-4-methoxy-6F(a-picolinylamino) -s-triazine.

(44) 2-methylthlo-d-neopentylamino-fi-(a-picolinylamino) -s-trlazine.

(45)2-azldo-4-sec-butylamiuo-6-[2-(N-methylpyrrolidinyl)-methylamlnol-s-triazine.

(46) 2-methoxy--isopropylamino6-[2-(N-lsoamylpyrrolldinyl)-methylaminol-s-triazine (47)2-butylamlno-4-methylthlb-fi-[2-(N-propylpyrrolidinyl)-methylamino1-s-triazine. (48)2-chloro-i-propylamino-fi-[Z-(N-ethylpiperitlinyl)-methylamlmfl-striazine. (49) 2-methoxy-4-rnethylamlno-6-[2-(N-lsopropylplperldiuyl) -methylamino1-s-triazlne. (50)2'isohexy1amino-4-methylthio-6[2-(N-methylpiperldinyl)-methylamino]-s-triazine.

The following procedure, which employs commercial- 1y available startingmaterials, can be taken as illustrative of the general method ofpreparation of the novel triazine herbicides of this invention. Themethod is presented schematically as follows:

I II

- Acetone 25 N N onasn ennui LNHGIL-(X NaOH The mole ratio of Compound Ito Compound 11 in the first reaction ranges from 1:1 to 1:2. In theevent that it is 1:1, there must be present at least one equivalent of abase such as sodium bicarbonate. Preferably, a ratio of one mole ofCompound I to two moles of 'Compund II is employed. The solvent can beeither 2-oxydiethanol monoglycene. Preferably, the solvent is ethanoland the temperature can range from 30 to 100 C., preferably from 50 to60 C.

These compounds are excellently suitable as active ingredients for weedkillers, both for the killing of weeds among cultivated plants(selective herbicides) as well as for the total elimination orinhibition of undesired plant growth (overall toxic herbicides). Theword weed here also means undesired cultivated plants, e.g., those whichhave been previously planted or those which are planted in neighboringareas. In addition, the diamino-s-triazine derivatives as defined above,also exert other inhibitory infiuenceson the plant growth and may beused, for example, for defoliation, acceleration of ripeness bydessication, e.g., in potato plants, also blossom thinning, retardationof blossoming, prolongation of the harvesting period and storingpropensities. Some of these compounds display strong fungicidalactivity.

As previously noted, the present diamino-s-triazine derivatives areuseful as pesticides, particularly as herbicides and fungicides. When soused, the biologically active compounds are preferably formulated with asuitable carrier or diluent or combinations thereof.

The term carrier or diluent as used herein means a material, which canbe inorganic or organic and synthetic or of natural origin, with whichthe active ingredient is mixed or formulated to facilitate its storage,transport, and handling and application to the plants to be treated. Thecarrier is preferably biologically and chemically inert and, as used,can be a solid or fluid. When solid carriers are used, they arepreferably particulate, granular or pelleted; however, other shapes andsizes of solid carrier can be employed as well. Such preferable solidcarriers can be natural occurring minerals although subsequentlysubjected to grinding, sieving, purification, and/or othertreatmentsincluding, for example, gypsum; tripolite; diatornaceousearth; mineral silicates such as mica, vermiculite, talc, andpyrophyllite;

clays of the montmorillonite, kaolinite, or attapulgite groups; calciumor magnesium limes, or calcite and dolomite, etc. Carriers producedsynthetically, as for example, synthetic hydrated silica oxides andsynthetic calcium silicates can also be used, and many proprietaryproducts of this type are available commercially. The carrier can alsobe an elemental substance such as sulfur or carbon, preferably anactivated carbon. If the carrier possesses intrinsic catalytic activitysuch that it would decompose the active ingredient, it is advantageousto incorporate a stabilizing agent, as for example, polyglycols such asdiethylene glycol, to neutralize this activity and thereby preventpossible decomposition of the diamino-s-triazine derivatives of thepresent invention.

For some purposes, a resinous or waxy carrier can be used, preferablyone which is solvent soluble or thermoplastic, including fusiblematerials. Examples of such carriers are natural or synthetic resinssuch as a comarone resin, rosin, copal, shellac, damar, polyvinylchloride, styrene polymers and copolymers, a solid grade ofpolychlorophenol such as is available under the registered trademarkArocolor, a bitumen, an asphaltite,

a wax for example beeswax or a mineral wax such as paraffin wax ormontan Wax, or a chlorinated mineral wax, or a microcrystalline wax suchas those available under the registered trademark Mikrovan Wax.Compositions comprising such resinous or waxy carriers are 75% andpreferably of at least about or mixtures of these two types of oil, areparticularly suitable liquid carriers.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carrier. One or more carriers, moreover, can be usedin combination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about to about90% by weight of the active ingredient, preferably from about 20 toabout 80 wt. percent. These concentrates can be diluted with the same ordifferent carrier to a concentration suitable for application. Thecompositions of this invention may also be dilute compositions suitablefor application. In general, concentrations of about 0.1 to about byweight, of active material based on the total weight of the compositionare satisfactory, although lower and higher concentrations can beapplied if necessary.

The compositions of this invention can also be formulated as dusts.These comprise an intimate admixture of the active ingredient and afinely powdered solid carrier such as aforedescribed. The powderedcarriers can be oiltreated to improve adhesion to the surface to whichthey are applied. These dusts can be concentrates, in which case ahighly sorptive carrier is preferably used. These require dilution withthe same or a different finely powdered carrier, which can be of lowersorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the active ingredient mixed with adispersing, i.e., defiocculating or suspending agent, and, if desired, afinely divided solid carrier and/or a wetting agent. The activeingredient can be in particulate form or adsorbed on the cartier andpreferably constitutes at least about 10%, more preferably at leastabout 25%, by weight of the composition. The concentration of thedispersing agent should in general be between about 0.5 and about 5% byweight of the total composition, although larger or smaller amounts canbe used if desired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e., deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can also possess wetting properties as well.

The dispersant 0r dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or a synthetic polymeric material suchas polyvinyl alcohol and methyl cellulose. Preferably, however, thedispersants or dispersing agents used are sodium or calcium salts ofhigh molecular weight sulfonic acids, as for example, the sodium orcalcium salts of lignin sulfonic acids derived from sulfite cellulosewaste liquors. The calcium or sodium salts of condensed aryl sulfonicacid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be non-ionic type surfactants, as forexample, the condensation products of fatty acids containing at least12, preferably 16 to 20, carbon atoms in the molecule, or abietic acidor naphthenic acid obtained in the refining of petroleum lubricating oilfractions with alkylene oxides such as ethylene oxide or propyleneoxide, or with both ethylene oxide and propylene oxide, as, for example,the condensation product of oleic acid and ethylene oxide containingabout 6 to ethylene oxide units in the molecule. Other nonionic wettingagents like polyalkylene oxide polymers, commercially known as Pluronicscan be used. Partial esters of the above acids with polyhydric alcoholssuch as glycerol, polyglycerol, sorbitol, or mannitol can also be used.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfom'c acidscontaining at least 10 carbon atoms in a molecule, for example, thesodium secondary alkyl sulfates,

6 dialkyl sodium sulfosuccinate available under the registered trademarkTeepol, sodium salts of sulfonated castor oil, sodiumdodecylbenzenesulfonate.

Granulated or pelleted compositions comprising a suitable carrier havingthe active ingredient incorporated therein are also included in thisinvention. These can be prepared by impregnating a granular carrier witha solution of the inert ingredient or by granulating a mixture of afinely divided solid carier and the active ingredient. The carrier usedcan consist of or contain a fertilizer or fertilizer mixture, as forexample, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active ingredient in an organic solvent or mixture of solvents,such as for example, alcohols; ketones, especially acetone; ethers;hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed oncrops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably havea flash point above 73 F., an example of this being a refined aromaticextract of kerosene. Auxiliary solvents such as alcohols, ketones, andpolyalkylene glycol ethers and esters can be used in conjunction withthese petroleum solvents.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions or dispersionof the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50% by volume, based on the total composition, to facilitatesubsequent dilution with water. Suitable organic liquids include, e.g.,the above petroleum hydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-in-water emulsions can be used,producing concentrates which can be diluted with relatively largevolumes of water for application by high volume spraying or relativelysmall volumes of water for low volume spraying. In such emulsions, theactive ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc., or dosage level, exposuretimes, test plants used, etc. by which the compounds and/or compositionsdescribed and claimed are prepared and/ or used.

EXAMPLE 1 Preparation of2,4-dichloro-6-tetrahydrofurfurylaminos-triazine A solution of 27.5 g.of tetrahydrofurfurylamine in 50 ml. of acetone was added to a stirredsolution of 25 g. cyanuric chloride in ml. of acetone at -10 to 20 over/2 hour. The mixture was stirred one hour at 10. The acetone was removedunder reduced pressure. The residue was taken up in 1 l. of chloroform,washed three times with 250 ml. of water, dried over magnesium sulfateand filtered. The chloroform was removed under reduced pressure and theresulting product was recrystallized from benzene-hexane affording 20.3g. of 2,4-dichloro-6-tetrahydrofurfurylamino-s-triazine, M.P. 98100 C.

Elemental analysis.-Calculated (percent): C, 38.57; H, 4.05; N, 22.49.Found (percent): C, 38.93; H, 4.26; N, 22.47.

EXAMPLE 2 Preparation of 2,4-dichloro-6-furfurylamino-s-triazine Theprocedure described in Example 1 was employed. The product,2,4-dichloro-6-furfurylamino-s-triazine, had

' 7 M.P. 106-108 C. The structure was verified by NMR and infrared.

. p 8 The identity of these compounds was established by NMR andinfrared spectroscopy and/ or elemental analysis.

TABLE 1 01 A i i R HN N NHCH R Analysis Calculated Found Compound M.P.,number R R degrees C H N C H N 11 CHCCHs): Oil Structure verified byNMR, IR

C(CHa 50. 43 7. 24. 51 50. 41 7. 27 M. 64 CH( 50. 43 7. O5 24. 51 50. 777.15 24. 26 H 44. 35 5. 79 28. 74 44. 75 5. 98 25. 23

20 cHrouufio 183-185 Structure verified by NMR, IR

26 CHZCH3 d0 195-197 Structure verified by NMR, IR C(CH3)3 .d0-..118-120 Structure verified by NMR, IR H -do 224-226 Structure verifiedby NMR, IR

13 P 185/1 mm.

EXAMPLE 5 EXAMPLE 3 Preparation of2-chloro-4-ethylarnino-6-tetrahydrofurfurylamino-s-triazine (No.

A solution of 51 g. of tetrahydrofurf urylamine in 175 ml. acetone wasadded over a period of minutes to 48 g. of2,4-dichloro-G-ethylarnino-s-triazine in 350 ml. of acetone at 15-20".The mixture was stirred one hour at The acetone was removed underreduced pressure. The residue was taken up in 3 l. of chloroform, washedthree times with 500 ml. of water, dried over magnesium sulfate, andfiltered. The chloroform was removed under reduced pressure affording 50g. of 2-chloro-4-ethylamino- 6-tetrahydrofurfuryl-s-triazine, M.P.165-1675 C.

Recrystallization from ether-hexane atforded material with M.P. 166-168C.

Elemental analysis.Calculate'd (percent): C, 46.60; H, 6.26; N, 27.18.Found (percent): C, 46.94; H, 6.57; N, 27.83.

EXAMPLE 4 A number of 2-chloro-s-triazines substituted with amines inthe 4 and 6 position were prepared utilizing the method described inExample 2. The compounds pre- Preparation ofZ-ethylamino-4-methylthio-6- tetrahydrofurfurylamino-s-triazine Asolution of 50 g. of sodium hydroxide in 800 ml. of methanol was cooledin a Dry Ice-acetone bath and charged with g. of methanethiol. Theresulting solution was added to a mixture of 200 g. of2-chloro-4-ethylamino-6-tetrahydrofurfurylamino-s-triazine in 600 ml.of methanol. The mixture was heated at 55 for 15 hours. The methanol wasremoved under reduced pressure. The residue was taken up in 1.5 l. ofxylene, washed three times with 250 ml. water, dried over magnesiumsulfate,

filtered. Removal of the xylene under reduced pressure aflForded 200 g.of a yellow viscous oil, 2-ethylamino-4-methylthio-6-tetrahydrofurfurylamino s triazine. Semicrystallinematerial obtained from a concentrated xylene solution had M.P. 62-67. A

Elemental analysis.Calculated (percent): C, 49.04; H, 7.11; N, 26.00.Found (percent): C, 49.00; H, 7.18; N, 26.13.

EXAMPLE 6 A number of 2-methylthio-s-triazines substituted with aminesin the 4 and 6 position were prepared utilizing the method described inExample 5. The compounds prepared and their physical properties arelisted in Table II. The identity of these compounds was established byNMR and pared and their physical properties are listed in Table I. 55infrared spectroscopy.

TABLE II N N R'HN-L N "NHGH2R Analysis Calculated Found Compound M.P.,number R B degrees C H N C H N 2 CH(CH3)2 0 Oil 50. 7. 47 24. 71 52. 597. 50 83 3 C(OHa)s Same as above Oil Structure verified by NMR, IR 4CH(OH3)CHZCH3 do Oil Structure verified by NMR, IR

5 do Oil Structure verified by NMR, IR

6 CH3 d0. Oil Structure verified by NMR, IR 22 CHzCHs o 88-92 Structureverified by NMR, IR.

9 EXAMPLE 7 Preparation of 2-ethylamino-4methoxy-6-tetrahydrofurfurylamino-s-triazine 10 EXAMPLE 11 Preparation of2-mercapto-4-isopropylamino-6- tetrahydrofurfurylamino-s-triazine Asolution of 19 g. of 2-chloro-4-isopropylamino-6- A Solution of 4 ofSodium mefllOXide in 25 Of 5 tetrahydrofurfurylamino-s-triazine in 240ml. of N,N- methanol was 8 f -P Y dimethylformamide was heated to 100. Asolution of 10 tetrahydrofurfurylammo-s-triazme 1n 10 ml. of methanol.of Sodium hydrosmfidfi hydrate in 25 1 of Water was The mlxture washeated at for hours- The {nethanol added dropwise. The resulting darkgreen solution was was remoYed under reduced pressure- T fes ldue Washeated at 100 for 1.5 hours, then at reflux for one hour. talfen p 111chloroform, Washed three times h Water, 10 The cooled mixture was pouredinto 1.2 l. of water and drled Over magneslum Sulfate, filtered- RemovalOf the filtered. The solid was dissolved in 500 ml. of chloroform,chloroform? under l'dllfwd p afforded 5 8- Of washed two times with 100ml. of water, dried over mag- V1SC11$, y P Y Y 6 tetfahydl'ofur' nesiumsulfate, and filtered. Removal of the chloroformfurYliimlllo5411321116.- under reduced pressure afforded 15.1 g. of2-mercapto-4- Elemental analysls-calculated (P C, 52-16; 15isopropylamino-6-tetrahydrofurfurylamino-s-triazine, M.P. H, 7.56; N,27.65. Found (percent): C, 51.75; H, 7.61; 20540 2739- EXAMPLE 12EXAMPLE 8 Preparation of 2 (methylthiomethylthio) 4 isopropyl- A numberof 2-methoxy-s-triazines substituted withammo'G'tetrahydrofurfurylammms'tnazme amines in the 4 and 6 positionwere prepared utilizing the A solution of 1.0 g. sodium hydroxide in 15ml. of water method described in Example 7. The compounds prewas addedto 6 g. of 2-mercapto-4-isopropylamino-6-tetrapared and their physicalproperties are listed in Table III. hydrofurfurylamino-s-triazine. Themixture was stirred for The identity of these compounds was establishedby NMR 15 minutes and was then treated dropwise with 4 g. of andinfrared spectroscopy and/or elemental analysis. chlorodimethylsulfidein 20 ml. of ethanol. The resulting TABLE III (I)CH; a RHNJ\\N/ NHCHzRAnalysis Calculated Found Compound M.P., number R R degrees C H N O H Ns CH(CH3); O Oil 53.91 7.92 26.20 54. 32 8.14 25.68

9 0H Sameasabove. Oil 55.89 7.58 25.07 55.98 7.27 25.08

21 Structure verified by NMR, IR

do 011 CH CH2CH3 192-196 Structure verified by NMR, IR s)s Oil Structureverified by NMR, IR 3 Structure verified by NMR, IR

EXAMPLE 9 Preparation of 2-azido-4-ethylamino-6-tetrahydrofurfurylamino-s-triazine Preparation of2-azido-4-isopropylamino-6 tetrahydrofurfurylamino-s-triazine Theprocedure described in Example 9 was employed. The product,2-azido-4-isopropylamino 6 tetrahydrofurfurylamino-s-triazine, had M.P.90-93 The structure was verified by NMR and infrared spectroscopy.

Elemental analysis.Calculated (percent): C, 47.47; H, 6.52; N, 40.26.Found (percent): C, 48.12; H, 6.82; N, 39.62.

mixture was heated at 70 for 3.5 hours. The solvents were removed underreduced pressure. The residue was taken up in 250 ml. of chloroform,washed two times with 50 ml. of water, dried over magnesium sulfate,filtered. Removal of the solvent afforded 5.5 g. of oily2-(methylthiomethylthio) 4 isopropylamino6-tetrahydrofurfurylamino-s-triazine. The structure of the product wasverified by NMR and infrared spectroscopy.

EXAMPLE l3 2- (methylthioethylthio)-4-isopropylamino-6-tetrahydrofurfurylamino-s-triazine The proceduredescribed in Example 12 was employed. The product,2-(methylthioethylthio)-4-isopropylamino-6-tetrahydrofurfurylamino-s-triazine, was a viscous oil. The structure wasverified by NMR and infrared spectroscopy.

TESTING PROCEDURES Representative diamino-s-triazine derivatives fromthose prepared in the previous examples were evaluated for preemergenceherbicidal activity in this example. The test procedure employed was asfollows:

Two flats seeded with six crops (cotton, soybean, alfalfa, corn, riceand oats) and six weeds (mustard, morning glory, Zinnia, crabgrass,barnyard grass, and foxtail) were sprayed with a formulation containingthe test chemical at a rate equivalent to 10, 5, or 4 lbs./ acre, asspecified p.p.m. Maneb is used as a standard in this test. A typicalManeb dilution series:

(2) Bean powdery mildewEradicant Step 1: Bean plants with fully expandedprimary leaves are inoculated with spores of the powdery mildew fungus(Erysiphe p olygoni) prior to application of test chemicals. Chemicalsare applied at a concentration of 200 p.p.m. using the same method as inthe early blight test above. After the spray has dried, the plants areremoved to the greenhouse and held for a period of 7l0 days at the endof which time the amount of mildew on the primary leaves is rated.Ratings are on a scale of -10, where O=no control, =100% control.Ratings of 8-10 in the primary test justify taking the chemical to thenext step.

Step 2: Same test as above, except that the minimum effect dose isdetermined in the dilution series of 100, 20 and 4 p.p.m. The standardfor this test is Karathane. Typical values for Karathane:

(3) Bean rustEradicant Step 1: Pinto bean plants with fully expandedprimary leaves are inoculated with spores of the bean rust fungus(Uromyces phaseoli) and incubated for 24 hours. Chemicals are thenapplied at a concentration of 200 p.p.m. using the same method as theearly blight test above. After the spray has dried, the plants areremoved to the greenhouse and held for a period of 7-10 days. At the endof this time, the amount of rust is rated on a scale of 0-10, where 0=nocontrol, l0=complete control. Compounds having an 810 rating pass tosecondary testing.

Step 2: Same test as above except that the minimum elfective dose isdetermined in a dilution series of 100, 20 and 4 p.p.m. The standard inthe test is Glyodin.

(4) Bean rustSystemic eradicant Step 1: Pinto bean plants are inoculated24 hours prior to use as above, and the soil in the pot is treated with20 ml. of a formulation of the test chemical at 200 p.p.m. The plantsare removed to the greenhouse and held for a period of 7-10 days, at theend of which time the amount of rust is rated on the same scale asabove. Compounds giving 8-10 ratings pass on to the next step.

Step 2: Same test as above except that the minimum effective dose isdetermined in a dilution series of 100, 20

P.p.m.: Control rating and 4 p.p.m. Plantvax is used as the commercialstandard 10 in this test. 20 8 The following table illustrates thefoliar fungicidal ac- 4 6 tivity of some of the test compounds.

X A l i I R NHCHzR FOLIAR FUNGICIDE ACTIVITY Bean rust Rate Early BeanNumber X R R p.p.m. blight mildew Spray Systemic 1 SCHa CHzCHa 200 10 2SCH; CH(CHa)2 200 10 5 SCH: 200 10 6 SCH; CH3 200 10 7 OCH: CHzCHa 200 510 s OCH; CH(CH3)2 200 4 10 7 l2 Cl C(CHa)a 200 l0 10 17 Na CH(CH3)2 20010 1O What is claimed is: 1. A compound of the formula:

where in X is Cl, N CH S, CH SCH S, CH SCH CH S, or (EH R is alkyl offrom 1 to 6 carbon atoms, cyclopropylmethyl or tetrahydrofurfuryl; and Ris 2. A compound according to claim 1, 2-ethylamino-4-furfurylamino-6-methylthio-s-triazine.

3. A compound according to claim 1, 2-ethylamino-4-furfurylamino-6-methoXy-s-triazine.

4. A compound according to claim 1 in which R is 8. A compound accordingto claim 4, 2-sec-butyl-amino- 4-methy1thio-6-tctrahydrofurfurylamino striazine.

9. A compound according to claim 4, 2-cyclopropylmethylamino4-mcthylthio6 tetrahydrofurfurylaminos triazine.

10. A compound according to claim 4, Z-mcthylamino-4-methylthio-fi-tetrahydrofurfurylamino-s-tgiazinc.

11. A compound according to claim 4, 2-cthylamino-4-methoxy-6-tetrahydrofurfuryamino-s-triazine,

12. A compound according to claim 4, 2-mcthoxy-4-isopropylamino--tetrahydrofurfurylamino-s-triazine.

13. A compound according to claim 4, Z-cyclopropylmethylamino-4-methoxy6 tetrahydrofurfurylaminmstriazine.

14. A compound according to claim 4, 2-chloro-4-ethylamino6-tetrahydrofurfurylamino-s-triazine.

15. A compound according to claim 4,2-ch'loro-4-isopropylamino-6tctrahydrofurfurylamino-s-triazine.

16. A compound according to claim 4, 2tert-butylamino-4chloro-6'tetrahydrofurfurylamino-s-triazine.

17. A compound according to claim 4,2-sec-butylamino-4-ch1oro-6-tctrahydrofurfurylamino-s-triazinc.

18. A compound according to claim 4,2-chloro-4-methylamino-6-tetrahydrofurfurylamino-s-triazine.

19. A compound according to claim 4, 2-chloro-4-cyclopropylmethylamino-G-tetrahydrofurfurylamino-s-triazine.

20. A compound according to claim 4,2-azido-4-ethylaminoG-tetrahydrofurfurylamino-s-triazine.

21. A compound according to claim 4, 2-azido-4-iso-'propylamino-6=tetrahydrofurfurylamino-s triazine.

References Cited UNITED STATES PATENTS JOHN M. FORD, Primary ExaminerUS. Cl. X.R. 71-93; 260-249.8

